DE101778C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

Of the theoretically possible mononitro derivatives of p-amidophenol ethers are to now known only those of the general constitution

NH,

NO ₁

OR

correspond to: the o-nitrophenetidine, which by treating the acet-p-phenetidine (phenacetin) with aqueous nitric acid and subsequent saponification of the o-nitrophenacetin formed is created (Hinsberg & Autenrieth, Archiv f. Pharm. 1891, p. 456).

The o-nitrbanisidine is obtained in an analogous manner from the acet-p-anisidine.

It has now been found that by nitriding - under different conditions - in sulfuric acid solution · - comes to nitro derivatives of amidophenol ethers, which the general constitution

NH ,,

OR

own. You get these nitro derivatives by dissolving the phenetidine BEZW. Anisidines in cone. Sulfuric acid and subsequent nitriding with a mixture of cone. Sulfuric acid and Nitric acid. It is more expedient to use their acetyl derivatives instead of the free bases go out to nitrate them, as mentioned, and to saponify the nitroacetyl derivatives. The latter Procedure has the advantage that it immediately leads to almost pure products.

Compared to the above-mentioned known o-nitro derivatives, these show m-nitroamidophenol ethers a characteristically different behavior. While the former of the general formula

NH ₁

OR

unable to form water-resistant salts, but from their solutions in cone. Acids are precipitated as free bases by water, show the m-nitro bodies of the general formula:

NH,

OR

very basic character and form

Salts which are scarcely dissociated even by hot water.

While the well-known o-nitroamidophenol ethers in diazotizing and coupling with j3-naphthol give red to bluish-red dyes, one obtains from the m-amidophenol ethers at orange-yellow shades of the same treatment, especially those with m-nitrophenetidine and β-naphthol produced dye on the fiber because of its excellent fastness properties and the convenience of the fiber not to be sublimated, should find commercial use (see patent no. 99338).

EXAMPLE I. Eighteen parts of phenacetin are dissolved in 80 parts of sulfuric acid (66 ° C.) and a mixture of 12 parts of nitric acid (36 ° C.) and 12 parts of cone. Sulfuric acid nitrated at 5 °. If this mixture is poured onto ice, the m-nitrophenacetin separates out as a light yellow precipitate. The same is dissolved in dilute sulfuric acid and heated ^{to 80 to 90 0 for a few hours.} On cooling, the sulphate of m-nitrophenetidine separates out as a thick crystalline paste of reddish color, and can be purified by recrystallization from hot water. When alkali is added to the solution of the sulfate, the free base precipitates as an orange-yellow oil, which solidifies on standing. Recrystallized from dilute alcohol several times, the m-Nitrophenetidin forms yellow needles, melting at 170 ^0, while the known o-Nitrophenetidin melts at 113 °. Example II. Acet 16 parts of p-anisidine are (66 ° B) dissolved in 80 parts of sulfuric acid and cone with a mixture of 12 parts of nitric acid (36 ⁰ B.) and 12 parts. Sulfuric acid nitrates. After pouring out onto ice, the m-nitroacet-p-anisidine separates out as a light yellow precipitate. The same is dissolved in dilute sulfuric acid and heated to 80 to 90 ° for a few hours. On cooling, the sulphate of m-nitro-panisidine separates out as a thick crystalline paste of reddish color, and can be purified by recrystallization from hot water. When alkali is added to the sulphate solution, the free base precipitates as a dark red oil, which solidifies after a while. By recrystallization from ether to obtain the m-nitroanisidine in red crystals which melt 50 against ^{the 0th} The homologous o-nitro-p-anisidine however, melts at 124 ^0th

Claims (1)

Patent Claim:. Process for the production of i-amido-3-nitro-4-phenol ethers, consisting in that p-amidophenol ethyl or methyl ether or their acetyl derivatives, in sulfuric acid dissolved, nitrated.